CN114709377B - High-nickel positive electrode material and preparation method and application thereof - Google Patents
High-nickel positive electrode material and preparation method and application thereof Download PDFInfo
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- CN114709377B CN114709377B CN202210319511.4A CN202210319511A CN114709377B CN 114709377 B CN114709377 B CN 114709377B CN 202210319511 A CN202210319511 A CN 202210319511A CN 114709377 B CN114709377 B CN 114709377B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 216
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 141
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 83
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000011247 coating layer Substances 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 19
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 10
- 239000002041 carbon nanotube Substances 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229910021385 hard carbon Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910021384 soft carbon Inorganic materials 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000007784 solid electrolyte Substances 0.000 claims description 6
- 239000002223 garnet Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005279 LLTO - Lithium Lanthanum Titanium Oxide Substances 0.000 claims description 4
- 239000002228 NASICON Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 42
- 239000003792 electrolyte Substances 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011664 nicotinic acid Substances 0.000 abstract description 8
- 230000002829 reductive effect Effects 0.000 abstract description 5
- 240000002853 Nelumbo nucifera Species 0.000 abstract description 4
- 235000006508 Nelumbo nucifera Nutrition 0.000 abstract description 4
- 235000006510 Nelumbo pentapetala Nutrition 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 2
- 230000037427 ion transport Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 37
- 239000010410 layer Substances 0.000 description 29
- 229910001416 lithium ion Inorganic materials 0.000 description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 27
- 230000002209 hydrophobic effect Effects 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 239000010406 cathode material Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 230000009286 beneficial effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 12
- 238000001694 spray drying Methods 0.000 description 12
- 238000000498 ball milling Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 9
- 238000009736 wetting Methods 0.000 description 9
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 230000036961 partial effect Effects 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000003075 superhydrophobic effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000003125 aqueous solvent Substances 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 238000003491 array Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 description 2
- 229910009511 Li1.5Al0.5Ge1.5(PO4)3 Inorganic materials 0.000 description 2
- 229910011410 LiNi0.6Co0.2Mn0.1O2 Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000005521 carbonaceous coating layer Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 2
- 229910052912 lithium silicate Inorganic materials 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 239000004890 Hydrophobing Agent Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- -1 etc. Chemical compound 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/32—Nickel oxide or hydroxide electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a high-nickel positive electrode material and a preparation method and application thereof, wherein particles of the high-nickel positive electrode material comprise a core, a plurality of columnar bulges which grow on the surface of the core in situ and extend outwards, and a coating layer arranged on the surface of the core, wherein the columnar bulges are dispersed on the surface of the core, the coating layer is coated on the surface of the core except the columnar bulges, and the columnar bulges of adjacent particles are staggered to form a meshing relationship; the inner core is made of high nickel anode material; the columnar bulge is made of at least one material selected from oxide, carbon tube or fiber which are electrochemically inactive and stable in structure; the coating layer is made of carbonaceous materials, and the bionic structure similar to lotus leaves is skillfully constructed on the surface of the material, so that the reactivity of water vapor or electrolyte at a high nickel interface can be effectively reduced, and the ion transport property of the material is not affected.
Description
Technical Field
The application relates to the technical field of secondary battery preparation, in particular to a high-nickel positive electrode material, a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, high output voltage, high output power and the like, and is widely applied to the fields of electronics, traffic, energy sources and the like. Particularly in the field of new energy automobiles, a lithium ion battery is one of the power energy storage technologies which are acknowledged to be the most promising. The core components of the lithium battery are positive electrode material, negative electrode material, electrolyte, diaphragm, and corresponding connected accessories and loops. The anode and cathode materials can release/intercalate lithium ions, so that energy storage and release are realized. The electrolyte is a carrier for lithium ions to pass between the positive and negative electrodes, and the nonconductive diaphragm can pass through the lithium ions, but separates the positive and negative electrodes to prevent short circuit. The positive and negative electrode materials are the main body part for playing the energy storage function, and the most direct manifestation of the energy density, the cycle performance and the safety performance of the battery core. Especially, the development of the anode material directly restricts the improvement of the endurance and safety performance of the new energy electric automobile. Therefore, development of high-performance, high-safety and low-cost cathode materials is one of the keys of research.
Ternary positive electrode materials with high nickel content (nickel content greater than 60%) are increasingly widely used in power batteries, and the existing bottlenecks are also of great concern. As the nickel content increases, the thermal stability of the material becomes poor; ni (Ni) 4+ The content becomes high, oxidation reaction is easy to occur, side reaction is easy to occur with electrolyte, and the battery cycle is attenuated, so that the safety performance is deteriorated. In addition, the high nickel material is easy to generate interface reaction in the manufacturing, storage and subsequent use processes, namely, the free lithium on the surface of the high nickel material and water and carbon dioxide in the air generate irreversible interface reaction, so that a plurality of practical problems, such as slurry gel formation, cell gas production, capacity attenuation, high-temperature storage failure, electrolyte consumption, irreversible phase change and the like, are caused.
At present, aiming at the problems of poor high-temperature storage, safety performance, cycle stability and processing performance of a lithium ion battery taking a high-nickel material as a positive electrode material, the problems are mainly inhibited and improved by modification means such as surface metal oxide coating, surface polymer coating, fast ion conductor coating, element doping, surface treatment (plasma, high-energy laser, chemical acid treatment and the like). Among them, the surface of the high nickel material is coated with organic and inorganic hydrophobic layers (CN 201410317277.7), conductive polymers (CN 105895877A), silane coupling agents (CN 108155352A), fluorine-containing alkyls (CN 108270010A) and the like, however, achieving an effective coating layer is difficult to achieve a compromise between material dynamics performance and cost.
CN101301598A discloses a hydrophobic treatment method for the surface of an inorganic powder material, wherein the inorganic powder material can be nickel cobalt lithium aluminate, cobalt nickel lithium manganate or nickel cobalt lithium ion battery anode material; the method comprises the steps of adopting a hydrophobic agent to treat an inorganic powder material to obtain wet powder; then drying the wet powder at 80-150 ℃; the hydrophobic treatment of the surface of the inorganic powder material is completed; wherein the hydrophobing agent is one or a mixture of alcohols, aldehydes, ketones, esters and silanes, which solves the problem that inorganic powder materials can absorb moisture in air when stored, transported and used under the atmospheric environment of normal temperature and pressure or under the condition of high humidity. Although the method provides a hydrophobic treatment method for the surface of the positive electrode material of the lithium ion battery, the method has limited hydrophobic materials, only carries out hydrophobic treatment on the surface of the material, does not form an effective coating layer, and is difficult to solve the side reaction of trace water in the material and electrolyte.
CN103392249a discloses a lithium ion secondary battery and a method for producing the same, which is characterized in that the battery comprises a positive electrode formed by using a composition containing an aqueous solvent, the positive electrode comprises a positive electrode current collector and a positive electrode mixture layer formed on the current collector, the positive electrode mixture layer contains at least a positive electrode active material and a binder, the surface of the positive electrode active material is coated with a hydrophobic coating film, the binder is a binder dissolved or dispersed in the aqueous solvent, and the hydrophobic coating film is formed of a hydrophobic resin, so that contact between the positive electrode active material and the aqueous solvent can be prevented. Although the method for hydrophobic treatment of the surface of the positive electrode material of the lithium ion battery is also provided, the method is limited to an aqueous solvent, and meanwhile, the surface of the positive electrode active material is simply coated with hydrophobic resin, so that the resistance of the positive electrode active material can be increased by the hydrophobic resin, and the transmission of electrons and ions is not facilitated.
CN102709591a discloses a lithium ion secondary battery, the positive electrode membrane comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector, the surface of the positive electrode membrane or the surface of the isolating membrane is coated with an organic water repellent coating, and the surface of the positive electrode membrane or the surface of the isolating membrane of the lithium ion secondary battery is coated with the organic water repellent coating, so that the water content in the lithium ion secondary battery can be effectively reduced, the side reaction caused by water in the working process of the lithium ion secondary battery is reduced, and the cycle performance and the storage performance of the lithium ion secondary battery are improved. However, in this method, the organic hydrophobic layer is coated on the positive electrode sheet, and the inside of the positive electrode active material is not coated with the organic hydrophobic layer, so that the hydrophobicity between the active materials is limited.
CN102583321A discloses a carbon nano tube/oxide composite film with high specific surface area and a preparation method thereof, wherein the specific surface area of the composite film is 100-1800m 2 And/g, the super-hydrophobic structure is a net structure, and the slender few-wall carbon nanotubes are mutually staggered to form a frame-like structure, which is lackThe trapped multiwall carbon nanotubes and oxides are mixed with each other and put into the space of the rack-like structure, so that the hollow carbon nanotubes can be applied to lithium ion batteries. However, how to use the composite film for a lithium ion battery does not involve the use of the composite film as a film structure for a lithium ion battery, and the coating effect cannot be formed on the surface of the positive electrode active material, so that the hydrophobicity between the active materials is also relatively limited.
CN201510628492.3 discloses a high nickel positive electrode material of lithium ion battery, which is a composite positive electrode material formed by coating modified super-hydrophobic material deposited with nano powder material on the surface of the high nickel positive electrode material of lithium ion battery, bridging particles of the high nickel positive electrode material of lithium ion battery by the modified super-hydrophobic material, and coating the high nickel positive electrode material of lithium ion battery with the modified super-hydrophobic material. However, how to coat the hydrophobic film and nano material particles on the surface of the positive electrode material effectively and uniformly to form a complete hydrophobic structure is difficult to ensure, and as a result, a porous coating layer with uneven distribution is possible, and the actual hydrophobic effect is limited.
Therefore, a coating layer which is uniformly coated and self-assembled to construct a super-hydrophobic micro-nano structure is developed, the surface hydrophobicity, the high ionic electron conductivity and the excellent electrochemical characteristics of the high-nickel positive electrode material are realized, the storage property, the safety and the cycle performance of the high-nickel positive electrode material of the lithium ion battery are greatly improved, and the technical support is provided for wider application of the high-nickel positive electrode material of the lithium ion battery.
Disclosure of Invention
The application aims to overcome the defects of the prior art, provide a high-nickel positive electrode material which can effectively reduce the reactivity of water vapor or electrolyte in a high-nickel interface without affecting the ion transport property of the material, and correspondingly provide a preparation method of the high-nickel positive electrode material and application of the high-nickel positive electrode material as a positive electrode material in a secondary battery.
In order to solve the technical problems, the application adopts the following technical scheme:
the high-nickel positive electrode material comprises a core, a plurality of columnar bulges which grow on the surface of the core in situ and extend outwards, and a coating layer which is arranged on the surface of the core, wherein the columnar bulges are dispersed on the surface of the core, and the coating layer is coated on the surface of the core except the columnar bulges;
the inner core is made of a high nickel positive electrode material; the columnar bulge is made of at least one material selected from oxide, carbon tube or fiber which are electrochemically inactive and stable in structure; the coating layer is composed of a carbonaceous material.
According to the application, a bionic structure similar to lotus leaves, namely a micro-nano columnar array, is skillfully constructed on the surface of the material, the structure remarkably increases the contact angle of the surface of the high-nickel material, forms a non-wetting structure with rough surface and a super-hydrophobic interface, forms a larger wetting angle for water vapor drops in air, effectively reduces the reactivity of water vapor at the high-nickel interface, and simultaneously blocks the contact between carbon dioxide in the air and the high-nickel interface, so that the failure interface reaction of the high-nickel material in the preparation, storage and processing processes is inhibited, and the material failure is avoided. Meanwhile, the inactive contact structures are uniformly distributed on the particle surfaces, so that the transport characteristic of ions is not affected, the reaction between electrolyte and interfaces is reduced, namely, the structural stability of the material is improved, and the dynamic characteristic is not sacrificed. In addition, the nano-protrusions among the particles are mutually meshed so as to increase the adhesive force of the pole piece.
Meanwhile, the micro-nano structure between the convex points forms capillary action, which is beneficial to electrolyte adsorption, electron conduction and ion transmission. The limited solid phase coating and the partial carbon coating are beneficial to reducing active reaction points, preventing excessive side reactions caused by direct contact of electrolyte and active substances, and being beneficial to the cycle stability and the safety characteristics of the battery. And the carbon coating layer can increase the electronic conductivity of the material, thereby being beneficial to improving the multiplying power characteristic.
The high-nickel positive electrode material has a core of LiNi x M y M’ z O 2 Wherein x is more than or equal to 0.6 and less than or equal to 1,0.0, y is more than or equal to 0.4,0.0 and less than or equal to z is more than or equal to 0.4, and x+y+z=1; m is one of Co, fe and Mn; m' is one or more of Mg, al, ca, ti, V, cr, mn, fe, ni, cu, zn, Y, zr, nb, B, la, P, F.
The solid electrolyte is perovskite type (LLTO), inverse perovskite type, NASICON typeGamnet type, halide, sulfide, li 3 N and its derivatives, li 2 O-B 2 O 3 System glassy state, li 4 SiO 4 A complex of one or at least two of the derivatives.
The oxide includes, but is not limited to, alumina, titania, silica, magnesia, or zirconia.
The oxide is preferably at least one of alumina and silica, and more preferably alumina.
The oxide may be one of the above oxides, or may be in the form of a heterostructure of two or more combinations, for example, a combination of alumina and silica, a combination of magnesia and zirconia, a combination of alumina, titania and magnesia, or the like.
The above high nickel positive electrode material preferably, the solid electrolyte includes, but is not limited to, perovskite type (LLTO), inverse perovskite type, NASICON type, garnet type, halide and sulfide, li 3 N and its derivatives, li 2 O-B 2 O 3 System glassy state, li 4 SiO 4 A derivative.
The solid electrolyte is preferably Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP)、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) garnet type Li 7 La 3 Zr 2 O 12 At least one of (LLZO), and preferably LATP.
In the above high nickel cathode material, preferably, the height of the columnar protrusion along the radial direction of the inner core is 50-1000nm, and the diameter of the columnar protrusion is 2-50nm.
The high nickel positive electrode material preferably has a thickness of 2-200nm
In the above high nickel cathode material, preferably, the coating layer is a carbon source cracking product.
The coating layer material is hard carbon, soft carbon, carbon nano tube and graphene formed by cracking a carbon source or a mixture of the hard carbon, the soft carbon, the carbon nano tube and the graphene; and can also be various hard carbon, soft carbon, carbon nano tube or graphene doped with nitrogen, sulfur, boron or phosphorus.
The coating layer is fully or partially converted into carbon dioxide in the secondary heat treatment process.
The high nickel positive electrode material is preferably a high nickel core, namely a nickel, cobalt and manganese ternary positive electrode material with nickel content more than or equal to 60%, a nickel, iron and aluminum ternary positive electrode and a nickel, manganese and boron ternary positive electrode.
The high-nickel positive electrode material of the lithium ion battery is at least one of nickel cobalt lithium aluminate, nickel cobalt lithium manganate, nickel lithium manganate or nickel lithium cobaltate. That is, only any one of lithium nickel cobalt aluminate, lithium nickel cobalt manganate, lithium nickel manganate or lithium nickel cobalt oxide may be selected, and may be in the form of a combination of two or more, for example, a combination of lithium nickel cobalt aluminate and lithium nickel cobalt manganate, a combination of lithium nickel manganate and lithium nickel cobalt oxide, a combination of lithium nickel cobalt manganate, lithium nickel cobalt aluminate and lithium nickel manganate, or the like.
In the above high nickel positive electrode material, the particle diameter of the core is preferably 5 to 100 μm.
The present application also provides a method for preparing the high nickel cathode material, which comprises the following steps:
s1: preparing high-nickel anode material particles with a carbon source coating layer, and performing first heat treatment on the obtained product in an oxygen-free atmosphere to enable the carbon source coating layer to undergo a cracking reaction, so that the coating layer with a porous structure is formed on the surface of the high-nickel anode material;
s2: and (2) placing the product obtained in the step (S1) in a columnar protrusion growth source solution, filling micropores of a coating layer by a coprecipitation or sol-gel method, and performing a second heat treatment to enable the surface of the inner core to generate a plurality of columnar protrusions in situ, wherein the columnar protrusions extend outwards from corresponding pores of the coating layer.
The application also provides an application of the high-nickel positive electrode material or the high-nickel positive electrode material prepared by the preparation method as a secondary battery positive electrode material.
Compared with the prior art, the application has the advantages that:
1. according to the high-nickel positive electrode material, the convex point (columnar) array of the bionic structure is constructed on the surface of the high-nickel positive electrode material particles, and the carbonaceous coating layers are filled between the convex points. The bump array can improve the contact angle of the material, form a non-wetting structure, slow down the erosion of water vapor and improve the processing performance; and the limited solid phase coating and the partial carbon coating are beneficial to reducing active reaction points, preventing excessive side reactions caused by direct contact of electrolyte and active substances, and being beneficial to the cycle stability and the safety characteristic of the battery. In addition, the carbon coating layer can also increase the electronic conductivity of the material, thereby being beneficial to improving the multiplying power characteristic.
2. According to the preparation method of the high-nickel positive electrode material, the carbon source coating layer on the surface of the high-nickel positive electrode material particles is cracked through heat treatment to form the porous carbon coating layer, then the columnar bulge grows at the position of the carbon coating layer removed from the surface of the high-nickel positive electrode material particles by skillfully utilizing a chemical principle, and the columnar bulge extends outwards from the pores of the carbon coating layer to grow, so that a coarse non-wetting structure is formed. The preparation method is simple and feasible, has low cost and wide application prospect.
Drawings
Fig. 1 is a schematic structural view of a high nickel cathode material according to the present application, wherein the left view is a schematic plan view, the middle view is a schematic cross-sectional view, and the right view is a schematic enlarged partial view.
FIG. 2 is a schematic diagram of a process for preparing a high nickel positive electrode material according to the present application;
FIG. 3 is a high-magnification SEM image of the high-nickel cathode material prepared in example 2;
FIG. 4 is a low magnification SEM image of the preparation of a high nickel positive electrode material of example 2;
FIG. 5 is a high-power SEM image of the high-nickel cathode material prepared in example 3;
FIG. 6 is a low magnification SEM image of the preparation of a high nickel cathode material of example 3;
FIG. 7 is a high-power SEM image of the high-nickel cathode material prepared in example 4;
FIG. 8 is a low magnification SEM image of the preparation of a high nickel cathode material of example 4;
fig. 9 is a cycle test chart of button cells of examples 1-6 and comparative examples;
fig. 10 cycle diagrams for the soft pack battery of examples 1-6 and comparative example;
wherein, the reference numerals in fig. 9 and 10 are respectively:
1-example 1, 2-example 2, 3-example 3, 4-example 4, 5-example 5, 6-example 6, 7-comparative example.
Detailed Description
The application will be further described with reference to the preferred embodiments.
The application mainly aims at the problems that the high-nickel material is easy to generate interface reaction in the manufacturing, storage and subsequent use processes, namely, the interface of the material and air with certain humidity generate irreversible interface reaction, so that various practical problems such as poor multiplying power performance, poor long-cycle stability and poor processability in the process of preparing slurry by the material are caused. Through fine structure design, a bionic structure similar to lotus leaves, namely a bump array, is constructed on the ternary core, and a non-wetting structure is formed on the surface. The interface water vapor reaction is inhibited, the dynamic characteristics are not influenced, and the structural stability and the dynamic characteristics of the material are solved.
As shown in fig. 1, the high nickel composite material with the bionic surface structure of the present application specifically includes:
1) Ternary high nickel structural core 1 (1-1 in schematic diagram 1);
2) Oxide bump array 1-2 on the surface of the inner core, diameter 1-50nm, height 50-1000nm (schematic diagram)
3) Carbon cladding layers 1-3 (partial enlarged view) between bump arrays, the thickness of the cladding layers being 2-200nm.
The method comprises the following steps:
the high nickel inner core 1-1 has the composition of LiNi x M y M’ z O 2 (x is more than or equal to 0.6 and less than or equal to 1,0.0, y is more than or equal to 0.4,0.0 and less than or equal to z is more than or equal to 0.4, and x+y+z=1), wherein M is one of Co, fe and Mn; m' is one or more of Mg, al, ca, ti, V, cr, mn, fe, ni, cu, zn, Y, zr, nb, B, la, P, F.
Only any one of nickel cobalt lithium aluminate, nickel cobalt lithium manganate, nickel lithium manganate or nickel lithium cobalt oxide may be selected, and may be in the form of a combination of two or more, for example, a combination of nickel cobalt lithium aluminate and nickel cobalt lithium manganate, a combination of nickel lithium manganate and nickel lithium cobalt oxide, a combination of nickel cobalt lithium manganate, nickel cobalt lithium aluminate and nickel lithium manganate, or the like.
As a further improvement of the application, the particle size of the high nickel positive electrode material is 5-100 μm.
As a further improvement of the present application, the high-nickel positive electrode material is a high-nickel positive electrode material having a coating layer on the surface and/or a doped high-nickel positive electrode material, preferably a high-nickel positive electrode material having a coating layer on the surface.
The bionic structure is formed into a 1-2 bump array:
the bump array is as follows: the electrochemically inactive, structurally stable oxides such as alumina, titania, silica, magnesia, zirconia, etc., or carbon tubes or carbon fibers, or a mixture of any one or at least two of the vertical two-dimensional materials, preferably any one or a mixture of at least two of alumina and silica, more preferably alumina.
It may also be in the form of a combination of two or more, for example, a combination of alumina and silica, a combination of magnesia and zirconia, a combination of alumina, titania and magnesia, and the like.
The bump array is as follows: perovskite (LLTO), inverse perovskite, NASICON, garnet, halide, sulfide, and Li 3 N and its derivatives, li 2 O-B 2 O 3 System glassy state, li 4 SiO 4 A fast ion conductor.
The solid electrolyte is preferably Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP)、Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) garnet type Li 7 La 3 Zr 2 O 12 At least one of (LLZO), more preferably LATP
1-3 is a coating layer of carbon material
The cladding layer between the carbonaceous material bump arrays is typically 2-200nm thick. The carbonaceous material is hard carbon, soft carbon, carbon nanotubes and graphene formed by cracking a carbon source, or a mixture of any two.
And can also be various hard carbon, soft carbon, carbon nano tube or graphene doped with nitrogen, sulfur, boron or phosphorus.
The preparation process of the high nickel composite material is shown in fig. 2, and comprises the following steps:
s1: 2-1 and 2-11 in FIG. 2, a carbon source coating layer is formed on the surface of the high nickel material;
s2: 2-2 and 2-22 in FIG. 2, cracking the carbon source by heat treatment to form a porous carbon coating;
s3: as shown in fig. 2-3 and 2-33, columnar protrusions are grown on the surface of the high-nickel material in the pores of the porous carbon coating layer, so that a rough structure similar to the lotus leaf surface is constructed on the surface of the high-nickel material, and the rough structure is non-wetting to water vapor and wetting to electrolyte.
S4: the carbon layer between the columnar projections is partially or entirely converted into carbon dioxide during the heat treatment to disappear.
Description of working principle based on material structure:
the application constructs the micro-nano bump array based on the bionic structure design to form a surface roughness structure, and the micro-nano bump array is non-wetting to water vapor. Therefore, in the process of preparing, storing and manufacturing the battery by the high-nickel material, the interface reaction is inhibited, and irreversible phase change is avoided; meanwhile, a carbon coating layer is arranged between the salient points, which is favorable for electrolyte adsorption, electron conduction and ion transmission. The limited solid phase coating and the partial carbon coating are beneficial to reducing active reaction points, preventing excessive side reactions caused by direct contact of electrolyte and active substances, and being beneficial to the cycle stability and the safety characteristics of the battery. In addition, the carbon coating layer can also increase the electronic conductivity of the material, and is beneficial to improving the multiplying power characteristic.
The application is further described below in connection with specific preferred embodiments, but it is not intended to limit the scope of the application.
Example 1:
the embodiment provides a high nickel composite material of an alumina bump array, which is used as a positive electrode material of a lithium ion battery and is assembled into a secondary battery.
1) Preparation of porous layer on surface of high-nickel material
1000g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the high nickel ternary material into SBR emulsion with the concentration of 5% and 10L, stirring for 4 hours, carrying out spray drying on the solution in spray drying equipment with the inlet temperature of 180 ℃ and the outlet temperature of 120 ℃ at the flow rate of 2L/hour to obtain a product, and carrying out heat treatment for 2 hours at 120 ℃ in nitrogen atmosphere to obtain the high nickel material coated with the porous carbon layer.
2) High nickel composite material with bump structure
And (2) stirring the high-nickel material coated with the porous carbon layer prepared in the step (1) in a meta-aluminate solution with the concentration of 0.1mol/L for 4 hours at the rotating speed of 400rmb, filtering, washing, drying, and carrying out secondary heat treatment at the temperature of 500 ℃ on the material obtained by drying in air to obtain the high-nickel composite material with the aluminum oxide bump structure, wherein carbon coating layers are arranged between bumps.
Method for manufacturing secondary battery
Mixing the composite material prepared in the step 2), a conductive agent Super-p, a binder PVDF (Suwei 5130) and NMP according to the mass ratio: 97.5:1.2:1.3:142, and uniformly stirring to obtain stable and uniform slurry, coating the surface of an aluminum foil, drying at 120 ℃ to obtain a positive electrode plate, matching with a commercial graphite negative electrode material, wherein the electrolyte is LiPF6 with the volume ratio of 1mol/L, the solvent EC to PC to DEC to EMC is 1:0.3:1:1, the diaphragm is a three-layer diaphragm of PP/PE/PP, the thickness is 12um, and a soft package laminated battery with the nominal capacity of 4.2Ah is manufactured and used for testing the full battery performance of the material. The soft package battery testing method comprises the following steps: 1) Standing for 10 minutes, 2) charging at a constant current of 0.1C until the voltage is 4.3V; 3) Constant voltage charging, which cuts off the current to 0.05C; 4) Standing for 10 minutes; 5) Constant-current discharge of 0.1C is carried out, and the voltage is 2.8V; 6) Standing for 10 minutes; 7) Repeating the steps 2-6; 500 times; 8) Ending the test.
Example 2:
the embodiment provides a high nickel composite material of magnesium oxide bump arrays, which is used as a positive electrode material of a lithium ion battery and is assembled into a secondary battery.
1) Preparation of porous layer on surface of high-nickel material
1000g of LiNi 0.6 Co 0.2 Mn 0.1 O 2 Adding the high nickel ternary material into SBR emulsion with the concentration of 5% and 10L, stirring for 4 hours, carrying out spray drying on the solution in spray drying equipment with the inlet temperature of 200 ℃ and the outlet temperature of 120 ℃ at the flow rate of 2L/hour to obtain a product, and carrying out heat treatment for 2 hours at 200 ℃ in nitrogen atmosphere to obtain the high nickel material coated with the porous carbon layer.
2) High nickel composite material with bump structure
And (2) stirring the high-nickel material coated with the porous carbon layer prepared in the step (1) in a magnesium nitrate solution with the concentration of 0.1mol/L for 2 hours at the rotating speed of 400rmb, filtering, washing, drying, and carrying out secondary heat treatment at the temperature of 500 ℃ on the material obtained by drying in the air to obtain the high-nickel composite material with the magnesium oxide bump structure.
SEM morphology graphs of the high nickel cathode material particles with the surface having the hydrophobic structure prepared in this example are shown in fig. 3 and 4.
Method for manufacturing secondary battery
The procedure of example 1 was followed, and the method for testing the soft pack battery was the same as in example 1.
Example 3:
the embodiment provides a high nickel composite material which is used as a positive electrode material of a lithium ion battery and is assembled into a secondary battery.
1) Preparation of porous layer on surface of high-nickel material
1000g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the high nickel ternary material into SBR emulsion with the concentration of 5% and 10L, stirring for 4 hours, carrying out spray drying on the solution in spray drying equipment with the inlet temperature of 150 ℃ and the outlet temperature of 120 ℃ at the flow rate of 2L/hour to obtain a product, and carrying out heat treatment for 2 hours at 200 ℃ in nitrogen atmosphere to obtain the high nickel material coated with the porous carbon layer.
2) High nickel composite material with bump structure
By Li 2 CO 3 As lithium source, al 2 O 3 As aluminum source, tiO 2 As titanium source, NH 4 H 2 PO 4 As a phosphorus source, the mixture was hand-milled in an agate mortar in a stoichiometric ratio for 5min, and put into a 50ml alumina ball milling pot for wet ball milling. The wet ball milling is carried out by taking zirconia ball milling beads with diameters of 1mm and 2mm as milling media, the mass ratio of the two ball milling beads is 1:1, the mass ratio of the total mass of the ball milling beads to the mass ratio of the materials is 3:1, absolute ethyl alcohol is taken as a grinding aid, and ball milling is carried out for 2 hours at the speed of 420 revolutions per minute to uniformly mix the raw materials. After ball milling, ball milling beads and materials are separated, and the materials are placed in a drying oven for drying. After the materials are completely dried, putting the materials into an alumina crucible, melting the materials for 2 hours at a high temperature of 1500 ℃, and obtaining a glassy precursor after water quenching, and carrying out ball milling for 6 hours by a wet method by the same method to obtain glassy precursor slurry (solid content is 5%)
The high nickel material of the coated porous carbon layer prepared in the step 1), the glassy state slurry prepared in the step 2) and ethanol are mixed according to the following steps of 1:1:1, stirring for 2 hours, filtering, washing, heating by microwaves at 900 ℃ in air atmosphere, preserving heat for 30 minutes, naturally cooling, and obtaining the high-nickel composite material with the surface bump structure.
SEM morphology graphs of the high nickel cathode material particles with the surface having the hydrophobic structure prepared in this example are shown in fig. 5 and 6.
Method for manufacturing secondary battery
The procedure of example 1 was followed, and the method for testing the soft pack battery was the same as in example 1.
Example 4:
1) Preparation of porous layer on surface of high-nickel material
1000g of LiNi 0.6 Co 0.2 Mn 0.1 O 2 Adding the high nickel ternary material into SBR emulsion with concentration of 5% and 10L, stirring for 4 hours, spray drying the above solution in spray drying equipment with inlet temperature of 200 ℃ and outlet temperature of 120 ℃ at flow rate of 2L/hour to obtain a product, and heat-treating at 200 ℃ for 2 hours in nitrogen atmosphere to obtain the high nickel material coated with the porous carbon layerAnd (5) material.
2) High nickel composite material with bump structure
Will 3 g GeO 2 Mixing and stirring 3 mL of 30% hydrogen peroxide and 97 g of deionized water to obtain a transparent solution, adding 100g of the porous carbon layer coated high-nickel material prepared in the step 1) into 400mL of the solution, stirring for 0.5 hour at the rotation speed of 400rmb, adding 100m L% of 5% boric acid solution, stirring for 1 hour at the rotation speed of 400rmb, filtering, washing, drying, and performing secondary heat treatment at the temperature of 500 ℃ in air to obtain the high-nickel composite material with the bump structure.
SEM morphology graphs of the high nickel cathode material particles with the surface having the hydrophobic structure prepared in this example are shown in fig. 7 and 8.
Method for manufacturing secondary battery
The procedure of example 1 was followed, and the method for testing the soft pack battery was the same as in example 1.
Example 5:
1) Preparation of porous layer on surface of high-nickel material
1000g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the high nickel ternary material into 10L SBR emulsion with the concentration of 5%, stirring for 4 hours, carrying out spray drying on the solution in spray drying equipment with the inlet temperature of 180 ℃ and the outlet temperature of 120 ℃ at the flow rate of 2L/hour to obtain a product, and carrying out heat treatment for 2 hours at 200 ℃ in nitrogen atmosphere to obtain the high nickel material coated with the porous carbon layer.
2) High nickel composite material with bump structure
The high nickel material of the coated porous carbon layer prepared in the step 1) is mixed with a mixed solution of magnesium nitrate and aluminum acetate with the total concentration of 0.1mol/L (wherein the molar ratio of magnesium, zinc and manganese is 1:1: 1) Stirring at 400rmb for 4 hr, filtering, washing, drying, and performing a second heat treatment at 500 deg.C in air to obtain high nickel composite material with composite oxide bump structure, wherein carbon coating layer is arranged between the bumps.
Method for manufacturing secondary battery
The procedure of example 1 was followed, and the method for testing the soft pack battery was the same as in example 1.
Example 6:
1) Preparation of porous layer on surface of high-nickel material
1000g of LiNi 0.8 Co 0.1 Mn 0.1 O 2 Adding the high nickel ternary material into 10L SBR emulsion with the concentration of 5%, stirring for 4 hours, carrying out spray drying on the solution in spray drying equipment with the inlet temperature of 180 ℃ and the outlet temperature of 120 ℃ at the flow rate of 2L/hour to obtain a product, and carrying out heat treatment for 2 hours at 200 ℃ in nitrogen atmosphere to obtain the high nickel material coated with the porous carbon layer.
2) High nickel composite material with bump structure
And (2) stirring the high-nickel material coated with the porous carbon layer prepared in the step (1) in a solution of lithium metasilicate with the total concentration of 0.1mol/L for 4 hours at the rotating speed of 400rmb, filtering, washing, drying, and performing secondary heat treatment on the dried material in air at 500 ℃ to obtain the high-nickel composite material with the salient point structure of lithium silicate, wherein a carbon coating layer is arranged between salient points.
Method for manufacturing secondary battery
The procedure of example 1 was followed, and the method for testing the soft pack battery was the same as in example 1.
Comparative example
Method for manufacturing secondary battery
LiNi 0.8 Co 0.1 Mn 0.1 O 2 The high-nickel ternary material, the conductive agent Super-p, the binder PVDF (Suwei 5130) and the NMP are mixed according to the mass ratio: 97.5:1.2:1.3:142, and uniformly stirring to obtain stable and uniform slurry, coating the surface of an aluminum foil, drying at 120 ℃ to obtain a positive electrode plate, matching with a commercial graphite negative electrode material, wherein the electrolyte is LiPF6 with the volume ratio of 1mol/L, the solvent EC to PC to DEC to EMC is 1:0.3:1:1, the diaphragm is a three-layer diaphragm of PP/PE/PP, the thickness is 12um, and a soft package laminated battery with the nominal capacity of 4.2Ah is manufactured and used for testing the full battery performance of the material.
The batteries prepared in examples 1 to 6 and comparative example were subjected to a set condition: temperature ± 25 ℃, humidity: 60% in air; under the same conditions, the capacitance (0.1C, v.s.Li, voltage range: 2.8-4.3V) was measured, and the following Table 1 shows the measurement results:
table 1 examples the capacity of the air placed changes with time
As shown in the table, the high-nickel positive electrode material particles with the surface having the hydrophobic structure prepared by the application have better stability in the placing process, and the capacity of the high-nickel positive electrode material particles is still kept above 90% after the high-nickel positive electrode material particles are placed for 4 weeks, while the capacity of the conventional high-nickel positive electrode material particles is reduced to below 80%, so that the high-nickel positive electrode material provided by the application has better stability and better processing performance.
Referring to fig. 9 and 10, when the high-nickel cathode material provided by the application is applied to a battery, the battery cycle performance is better than that of a battery adopting a traditional high-nickel cathode material, and in particular, the high-nickel cathode material provided by the application is characterized in that a bump (columnar) array with a bionic structure is constructed on the surface of high-nickel cathode material particles, and a carbonaceous coating layer is filled between the bumps. The bump array can improve the contact angle of the material, form a non-wetting structure, slow down the erosion of water vapor and improve the processing performance; and the limited solid phase coating and the partial carbon coating are beneficial to reducing active reaction points, preventing excessive side reactions caused by direct contact of electrolyte and active substances, and being beneficial to the cycle stability and the safety characteristic of the battery. In addition, the carbon coating layer can also increase the electronic conductivity of the material, thereby being beneficial to improving the multiplying power characteristic and further meeting the application requirements better.
The present application is not limited to the above embodiments, but is capable of other modifications and variations within the scope of the application as defined by the appended claims.
Claims (9)
1. The high-nickel positive electrode material is characterized in that the high-nickel positive electrode material particles comprise an inner core, a plurality of columnar protrusions fixed on the surface of the inner core and extending outwards, and a coating layer arranged on the surface of the inner core, wherein the columnar protrusions are dispersed on the surface of the inner core, the coating layer is coated on the surface of the inner core except the columnar protrusions, and the columnar protrusions of adjacent particles are staggered to form a meshing relationship;
the inner core is a high nickel ternary core;
the columnar bulge is composed of solid electrolyte or oxide material which is electrochemically inactive and stable in structure;
the coating layer is made of a carbonaceous material;
wherein the height of the columnar bulge along the radial direction of the inner core is 50-1000nm, and the diameter of the columnar bulge is 1-50nm.
2. The high nickel positive electrode material according to claim 1, wherein the high nickel positive electrode material core is LiNi x M y M' z O 2 Wherein x is more than or equal to 0.6 and less than or equal to 1,0.0, y is more than or equal to 0.4,0.0 and less than or equal to z is more than or equal to 0.4, and x+y+z=1; m is one of Co, fe and Mn; m' is one or more of Mg, al, ca, ti, V, cr, mn, fe, ni, cu, zn, Y, zr, nb, la.
3. The high nickel positive electrode material according to claim 1, wherein the solid electrolyte is perovskite (LLTO), inverse perovskite, NASICON, garnet, halide and sulfide, li 3 N and its derivatives, li 2 O-B 2 O 3 System glassy state, li 4 SiO 4 A complex of one or at least two of the derivatives.
4. The high nickel positive electrode material according to claim 1, wherein the oxide is any one or a composite of at least two of alumina, titania, silica, magnesia, and zirconia.
5. The high nickel positive electrode material according to claim 1, wherein the carbonaceous material is hard carbon, soft carbon, carbon nanotubes or graphene, or a mixture of any two thereof; or hard carbon, soft carbon, carbon nanotubes or graphene doped with nitrogen, sulfur, boron or phosphorus.
6. The high nickel positive electrode material according to claim 1, wherein the thickness of the coating layer is 2 to 50nm.
7. The high nickel positive electrode material according to claim 1, wherein the particle diameter of the core is 5 to 100 μm.
8. A method for producing the high nickel positive electrode material according to any one of claims 1 to 7, comprising the steps of:
s1: preparing a high-nickel anode material shell-core structure with an organic coating layer, and performing first heat treatment on the obtained product in inert atmosphere to shrink and pyrolyze the organic coating layer, so as to form a coating layer with a porous structure on the surface of the high-nickel anode material shell-core structure;
s2: and (3) placing the product obtained in the step (S1) into a solution of a columnar bulge growth source, depositing in pores of a coating layer, and then performing a second heat treatment.
9. Use of the high nickel positive electrode material according to any one of claims 1 to 7, or the high nickel positive electrode material produced by the production method according to claim 8 as an electrode for a secondary battery positive electrode and a device for producing the same.
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